Process of preparing unsymmetrical 1:2-cobalt complexed azo compounds



United States Patent 3,356,671 PRESS @F PREPARHNG UNSYMMETRECAL 1:2- CQBALT CGMPLEXED AZO COMPOUNDS Alan Johnson, Peter Albert Mack, and Raymond Price, Manchester, England, assignors to Imperial Chemical industries Limited, London, England, a corporation of Great Britain No Drawing. Filed Mar. 17, 1965, Ser. No. 440,641 4 Claims. (Cl. 260145) ABSTRACT OF THE DllSCLOSURE Process for producing unsymmetrical 1:2-cobalt complexes containing one atom of cobalt in complex union with two different metallisable azo compounds by reacting a 1:1-cobalt complex of the formula with a metallisable azo compound of the formula z"r rr AN=N B to form said 1:2-cobalt complex having the formula wherein A and A each independently represent phenylene or naphthalene radicals; Z and Z", which are attached to A and A, respectively, in orthoposition to the azo group, independently represent O or COO; B and B each independently represent radicals of coupling components selected from the group consisting of phenol, naphthol, acylacetarylamide or S-pyrazolone series, the cobalt being attached to B and B" through the oxygen atoms which are situated in orthoposition to the coupling position; R R and R each independently represent a molecule of ammonia or a primary, secondary or tertiary monoamine; and wherein at least one of A, B and Z' is not identical with A, B and Z. The reac tion is carried out at a pH between 7.0 and 9.0.

This invention relates to a manufacturing process and more particularly it relates to an improved process for the manufacture of 1:2-c0balt complexes of metallisable azo compounds.

Although unsymmetrical 1:2-cobalt complexes formed from 1 atom of cobalt with a molecule of each of two different metallisable azo compounds have previously been described, the only method described for the preparation of such complexes has involved treating a mixture of two different metallisable azo compounds with a cobalting agent. However this method results in the formation of a mixture of complexes since not only is the required unsymmetrical complex obtained but there are also obtained the two symmetrical complexes containing 1 atom of cobalt in complex union with two molecular proportions of the same metallisable azo compound.

It has now been found that unsymmetrical 1:2-cobalt complexes containing 1 atom of cobalt in complex union with two different metallisable azo compounds can be readily obtained in a pure state free from the presence of undesirable symmetrical complexes.

3,356,67l Patented Dec. 5, 1967 According to the invention there is provided an improved process for the manufacture of the 1:2-cobalt complexes which are represented by the formula:

wherein A and A" each independently represent phenylene or naphthylene radicals which may contain further substituents; Z and 2', which are attached to A and A" respectively in ortho position to the azo group, each independently represent -O or -COO-; B and B each independently represent the radicals of coupling components which couple in ortho position to a hydroxy group or in vicinal position to an enolised keto group, the cobalt atom being attached to B and B" through the oxygen atoms which are in ortho or vicinal position to the coupling positions, provided that at least one of A, B and Z is not identical with A, B and Z respectively, which comprises reacting a 1:1-cobalt complex of the formula:

Formula I wherein R R and R each independently represent a molecule of ammonia or of a primary, secondary or tertiary monoamine, the coordinate bonds which link the co balt atom to the molecules of ammonia or the said amine being bonded to the nitrogen atoms present in the ammonia or amines with a metallisable azo compound of the formula:

wherein A, A", B, B, Z and Z stated.

The process of the invention can be conveniently carried out by stirring the reactants together in water, or in an organic liquid which is preferably a water-soluble organic liquid, or in a mixture of water and a watermiscible organic liquid, preferably at a temperature between 20 C. and the boiling point of the'medium in which the reaction is being carried out. The resulting 1:2- cobalt complex can then be isolated by conventional means, for example by adding sodium chloride to precipitate the complex which is then filtered off.

The process of the invention is preferably carried out under mildly alkaline conditions, for example at a pH between 7.0 and 9.0, by adding an alkali or an alkaline salt such as sodium carbonate or disodium hydrogen phosphate.

As examples of water-soluble organic liquids there may be mentioned ethanol, acetone, formamide, dioxan and B-ethoxyethanol.

In some cases it is advantageous to add a catalyst such as active carbon to ensure that the reaction proceeds to completion.

As examples of additional substituents which may be present in the phenylene or naphthylene radicals represented by A and A, and which may also be present in the coupling components B and B, preferably attached to phenyl or naphthyl radicals present in the said coupling components, there may be mentioned chlorine or bromine atoms; or lower alkyl in particular methyl; lower alkoxy in particular methoxy; nitro; cyano; lower alkylsulphoue such as methylsulphone and ethylsulphone:

have the meanings hydroxy lower alkylsulphone such as hydroxyethylsulphone; carboxylic acid; sulphonicacid; amino; substituted amino such as phenylamino, sulphophenylamino and N- lower alkylamino for example methylamino and dimethylamino; sulphonamide; substituted sulphonamide such as N lower alkyl and N-(hydroxy lower alky-Dsulphonamide for example N-methylsulphonamide, NzN-dimethylsulphon-amide, N-B-hydroxyethylsulphonamide and NrN- di(fi-hydroxyethyl)sulphonamide; and acylamino roups such as formylamino, acetylamino, benzoylamino, benzenesulphonylamino, carbomethoxyamino and carboethoxyamino groups.

Throughout this specification the terms lower alkyl and lower alkoxy are used to denote alkyl and alkoxy radicals respectively containing from 1 to 4 carbon atoms.

The lzl-cobalt complexes of Formula I may themselves be obtained by reacting a metallisable azo compound of the formula with a cobaltous complex of a cobaltous salt with ammonia or with a primary, secondary or tertiary monoamine, the reaction being performed in aqueous medium or in a mixture of water and a Water-miscible organic liquid, and preferably in an inert atmosphere.

The said cobaltous complex of a cobaltous salt can be obtained by treating a cobaltous salt, such as cobaltous acetate, chloride, sulphate or nitrate, with ammonia or with the said amine, preferably in an inert atmosphere.

As examples of the said primary, secondary or tertiary monoamines there may be mentioned primary and secondary alkylamines such as methylamine, dimethylamine, ethylamine, diethylarnine, di-n-propylamine, n-propylamine, iso-propylamine and n-butylamine; aromatic Primary and secondary monoamines in particular monoamines of the bermene and naphthalene series such as aniline, N-methylaniline, p-toluidine, a-naphthylamino and p-anisidine; and heterocyclic compounds containing a secondary or tertiary nitrogen atom as part of the heterocyclic ring such as pyridine, piperidine, isoquinoline, quinoline, p-picoline, morpholine and y-picoline. It is however preferred to use ammonia.

The metallisable azo compounds of Formulae II and III may themselves be obtained by coupling a diazotised primary amine of the benzene or naphthalene series which contain a hydroxy or carboxy group in ortho position to the amino group with a coupling component which couples in ortho position to a hydroxy group or in vicinal position to an enolised or enolisable keto group.

The said coupling components may be members, of any of the known series of coupling components which couple in ortho position to a hydroxy group or in vicinal position to an enolised or enolisable keto group, but preferably they are coupling components of the phenol, naphthol, acylacetarylamide or S-pyrazolone, in particular l-aryl-S-pyrazolone series.

As specific examples of the said primary amines there may be mentioned 2-aminophenol,

4- or 5-nitro-2-aminophenol,

4- or S-chIoro-Z-aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-chloro-2-aminophenol-6-sulphonic acid, 6-chloro-2-aminophenol-4-sulphonic acid, 4-nitro-2-aminophenol-6-sulphonic acid, 6-nitro-2-aminophen0l-4sulphonic acid, 2-arnin0phenol-4 6-disulphonic acid,

4 6-dinitro-2-aminophenol, 2-aminophenol-4-sulphon-N-/3-hydroxyethylamide, 2-aminophenol-4-B-hydroxyethylsulphone, 6-acetylamino-Z-aminophenol-4-sulphonic acid,

4-acetylamino-Z-aminophenol-6-sulphonic acid,

4-methyl-2-aminophenol,

4-methoxy-2-aminophenol,

2-aminophenol-4-sulphon-N-methylamide,

2-aminophenol-S-sulphonamide,

4-chloro-2-arninopheno1-5- or 6-sulphonamide,

Z-aminophenol-4-sulphon-N:N-dimethylamide,

2-aminophenol-4-methylsulphone,

Z-aminophenol-4-ethylsulphone,

anthranilic acid,

2-amino-3-naphthoic acid,

4- or S-chloro-anthranilic acid,

4- or S-nitroanthranilic acid,

4- or S-acetylamino-anthranilic acid,

4- or 5-sulphoanthranilic acid,

anthranilic acid 4-sulphonamide,

anthranilic acid 4- or 5-fl-hydroxyethylsulphone,

anthranilic acid 4- or S-ethylsulphone,

4- or S-benzoylaminoanthranilic acid,

3 3'-dihydroxy-4 4'-diamino diphenyl,

2-amino-1-naphthol-4: 8-disulphonic acid,

1-amino-2-naphthol-4-sulphonic acid,

l-amino-2-naphthol-4-sulphonarnide,

2-aminophenol-4- or 5-sulph0nic acid,

6-nitro-1-amino-2-naphthol-4-sulphonic acid,

6-acetylamino-l-amino-2-naphthol-4-sulphonic acid, and

2-(3-sulphoanilino)7-(2"-hydroxy-4"-sulpho-6"- aminophenylazo -8-naphthol-6sulphonic acid.

As specific examples of the said coupling components there may be mentioned phenols such as p-cresol,

3 :4-dimethylphenol,

2 :4-dimethylphenol,

2- or 3-acetylamino-4-methylphenol, 4-t-butylphenol,

2-hydroxy-5 6 :7 :'8-tetrahydronaphthalene,

v 2-hydroxy-3-sulphonic acid-5 :6 :7 8-tetrahydronaphthalene, 2-carboethoxyamino-4methylphenol, resorcinol, m-aminophenol, 2 4-dihydroxyacetophenone, 2 4-dihydroxyazob enzene, 2:4-dihydroxyazobenzene-2- or 4-sulphonic acid, 2 4-dihydroxyazobenzene-2 5'-disulphonic acid, 2:4-dihydroxy-4'-nitroazobenzene, 212' 4-trihydroxyazobenzene-3 5-disulphonic acid, 2:4-dihydroxy-4'- or -5'-(acetylamino)azobenzene-2- sulphonic acid and 4- (2" 4"-dihydroxyphenylazo-4'-nitrostilbcue-2 :2-

disulphonic acid; naphthols such as Z-naphthol, 1 :3- or 1 :S-dihydroxynaphthalehe, 2-naphthol-6-sulphonic acid, 1 18-dihydroxynaphthalene-3 :6-disulphonic acid, 1:3-dihydroxynaphthalene-5-, 6- or 7-sulphonic acid, 1 :3-dihydroxynaphthalene-5 7-disulphonic acid, 2-naphthol-6-sulphonamide, 2-naphthol-6-fi-hydroxyethylsulphone, 1-amino-4-naphthol, 2-amino-6-napht.hol, 1-amino-7-naphthol, 1-acetylamino-4-naphthol, 1-acetylamino-7-naphthol, l-propionylamino-7-naphth,ol, 1-carbomethoxyamino-7-naphthol, 1-carboethoxyamino-7-naphthol, 1-carbopropoxyamino-7-naphthol, Z-arnino-5-naphthol-7-sulphonic acid, Z-amino-S-naphthol-l :7-disulphonic acid, Z-acetylamino-S-naphthol7-sulphonic acid, 2-benzoylamino-5-naphthol-7-sulphonic acid, Z-phenylamino-5-naphthol-7-sulphonic acid,

2-(3-sulphoanilino)-5-naphthol-7-sulphonic acid, 2-amino-8-naphthol-6-sulphonic acid, Z-acetylamino-8-naphthol-6-sulphonic acid, 2(3'-or 4'-aminobenzoylamino) -5-naphthol-7-sulphonic acid,

2-(3'- or 4'-aminobenzoy1amino)-8-naphthol-6-sulphonic acid,

1-(3'- or 4'-amino-benzoylamino)-8-naphthol-3 :6-disulphonic acid,

2-(3- or 4-aminoanilino)-5-naphthol-7-sulphonic acid,

2-(3'- or 4'-amin0anilino) -8-naphthol-6-sulphonic acid,

1- 3 or 4'-aminoanilino) -8-naphthol-3 6-disulphonic acid,

2- 3'-amino-4'-sulphonanilino) -5-naphthol-7-sulphonic acid,

Z-phenylamino-8-naphthol-3 :6-disu1phonic acid,

2-(4'-a.mino-3'-sulphonanilino)-5-naphthol-7-sulphonic acid,

2- (4'-amino-3 '-sulphoanilino) -8-naphthol-6-sulphonic acid,

1-amino-8-naphthol-326-, -2:4- or -4:6-disulphonic acid,

1-amino-8-naphthol-4-sulphonic acid,

l-amino-S- naphthol-7-sulphonic acid,

1-acetylamino-8-naphthol-3 :6- or -4:6- disulphonic acid,

1-benzoylamino-8-naphthol-3:6 or -4:6-disulphonic acid,

1-phenylamino-8-naphthol-3:6- or -4:6-disulphonic acid,

1-naphthol-4-sulphonic acid,

1-naphthol-4:6-disulphonic acid,

2-naphthol-6:8-disulphonic acid,

l-naphthol-S-sulphonic acid,

2-naphthol-3 z6-disulphonic acid,

2-naphthol-3 6 8-trisulphonic acid,

1-amino-8-naphthol-4-sulphonic acid,

2-amino-8-naphthol-3 :6-disulphonic acid,

6-acetyl-2-naphthol,

4-acetyl-2-naphthol,

4-acetyl-1-naphthol,

1-naphthol-3-, -4- or S-sulphonamide,

2-naphthol-3-, -4-, -5-, -6, -7- or -8-sulphonamide,

5 8-dichlor-1-naphthol,

2-methylamino-5-naphthol-7-su1phonic acid,

2-methylamino-8-naphthol-6-sulphonic acid,

1-butyla1mino-8-naphth0l-3 :6-disulphonic acid,

1-naphthol-3 6-8-trisulphonic acid,

G-fl-hydroxyethylsulphonyl-Z-naphthol-3-sulphonic acid,

1-naphthol-3:6- or 3:8-disulphonic acid,

2-(4'-nitrophenylazo) -1-amino-8-naphthol-3 6-disulphonic acid,

2- (2'- or 4-sulphophenylazo) -1-amino-8-naphthol-3 6- disulphonic acid,

2-(2' :5-disulphophenylazo)-1-amino-8-naphthol-3 6- disulphonic acid, and

2-naphthol-7- or -8-sulphonic acid;

heterocyclic components such as barbituric acid and 2:4-

dihydroxyquinoline; 5-pyrazolones such as 1:3-dimethyl- S-pyrazolone, but more particularly 1-ary1-5-pyrazolones such as 1-phenyl-3-methyl-5-pyrazolones,

l-(2'- or 3'- or 4'-methylphenyl)-3-methyl-5-pyrazolone,

1-(2- 3- or 4'-sulphophenyl)-3-methy1-5-pyrazolone,

1-[3- or 4- (fl-hydroxyethylsulphonyl)phenyl] -3-methy1- 5-pyrazolone,

1-pheny1-3-carboxy-5-pyrazolone,

1(3'- or 4'-aminophenyl)-3-methyl-5-pyrazolone,

1- 2'-amethoxyphenyl) -3-methyl-5-pyrazolone,

1-(2-, 3- or 4-chlorophenyl)-3-methyl-5-pyrazolone,

1-(3'- or 4'-aminophenyl)-3-carboxy-5-pyrazolone,

1-(3-amino-4'-sulphophenyl) -3-(carboxy or methyl) S-pyrazolone,

1-(4'-amino-3-sulphophenyl) -3-(carboxy or methyl) -5- pyrazolone,

1-(2-, 3- or 4'-nitrophenyl) -3-methyl-5-pyrazolone,

1-(2':5'- or 3:4'-dichlor0phenyl)-3-methyl-5-pyrazolone,

1-(2-, 3' or 4'-sulphamylphenyl-3-methyl-5-pyrazolone,

1-(2-, 3' or 4'-methylsulphonylphenyl)-3-metl1yl-5- pyrazolone,

1-pheny1-5-pyrazoIlone-3-carboxycresidide,

1-phenyl-5-pyrazolone-3-carboxy-2'-toluidide,

1-phenyl-5-pyrazolone-3-carboxyanilide,

1:3-diphenyl-5-pyrazolone, 1-(2'-, 3- or 4'-N-methylsulph amylphenyl) -3 -methyl-5-pyrazolone,

1- 6'-chloro-3'-methyl-4-sulphophenyl) -3 methyl-5- pyrazolone,

1- (2 :5'-dich1oro-4'-sulphopheny1) -3 -methyl-5-pyrazolone,

1- 2'-methyl-5 '-sulphophenyl) -3 -methyl-5-pyrazolone,

1- (4-chloro-2-sulphophenyl) -3 -methyl-5-pyrazolone,

1- 6'-chloro-4'-sulpho-2-methylphenyl) -3-carboethoxy- S-pyrazolone,

1- (2' 5'-disulphophenyl) -3 -methyl-5 -pyrazo1one,

1- (4-sulphophenyl) -3-carb oxy-S-pyrazolone,

1-(2'-, 3- or 4'-carboxyphenyl)-3-methyl-5-pyrazolone,

1- 6--chloro-4'-sulpho-2'-methylphenyl) -3 -methyl-5- pyrazolone and 3carboxy-5-pyrazolone and acylacetarylamides in particular acetoa'cetanilides and =benzoylacetanilides such as acetoacet-4- (fi-hydroxyethylsulphonyl) -anilide, acetoacet-o-anisidide,

acetoacet-o-toluidide, acetoocet-o-chloranilide,

acetoacetanilide-3- or -4-sulphonic acid, acetoacet-3- or 4-aminoanilide, acetoacet-m-xylidide,

acetoacetanilide-2-, -3- or -4-carboxylic acid, benzoylacetanilide-3- or -4-sulphonic acid, benzoylacet-3- or -4-aminoanilide and acetoacetanilide-4-sulphonamide.

A preferred class of 1:2-cobalt complexes obtained by the process of the invention are those complexes which contain a single sulphonic acid group attached to one of the radicals represented by A, A", B and B.

The 1:2-cobalt complexes obtained by the process of the invention are valuable as intermediates in the production of other cobalt-containing azo dyestuffs, for example they can be converted to reactive dyestuffs by the introduction, by standard known methods, of reactive groups. The 1:2-cobalt complexes are also valuable in their own right as dyestulfs for textile materials such as cellulose textile materials, aromatic polyester textile materials, cellulose acetate textile materials, polyacrylonitrile textile materials, but more especially synthetic polyamide textile materials such as textile materials comprising polyhexamethyleneadipamide and polymers from caprolactam, and preferably natural polyamide textile materials such as woollen textile materials, and also leather.

The 1:2-cobalt complexes can be applied to textile materials by any of the processes known for applying such complexes to textile materials. Thus, for example, the textile materials can be dyed in a dyebath comprising an aqueous solution or suspension of one or more of the said complexes. If desired the dyebath can contain the usual additives such as organic acids, for example formic acid or acetic acid, neutral electrolytes such as sodium chloride or sodium sulphate, and cationic, anionic and/ or non-ionic surface-active agents.

When applied to polyamide textile materials the 1:2- cobalt complexes obtained by the process of the invention have excellent build-up properties and yield level yellow to black colourations possessing excellent fastness to light and to wet treatments such as washing, potting, milling and cross-dyeing.

The invention is illustrated but not limited by the following examples in which the parts are by weight.

Example 1 A mixture of 22.35 parts of the lzl-cobalt complex of 1-phenyl-3-rnethyl-4-(2-hydroxy-5' nitrophenylazo) 5- pyrazolone containing coordinated ammonia molecules,

21.95 parts of 1-(2-hydroxy-4-sulpho-6-nitronaphth-1'- ylazo)-2-naphthol, 500 parts of water and 1000 parts of formamide is adjusted to a pH of 8.0 by the addition of sodium carbonate, and the mixture is then stirred at 60 C. for 1 hour. The mixture is filtered, the resulting filtrate is poured into a solution of 1000 parts of sodium chloride in 4500 parts of water, and the precipitated solid is filtered off, washed with an aqueous solution of sodium chloride and dried.

The compound so obtained consists of the lz2-cobalt complex of the formula:

l- I l'Oz When applied to wool frorna neutral or slightly acid dyebath the complex yields reddish-brown shades possessing excellent fastness to light and to wet treatments. The 1:1-complex used in the above example was itself obtained as follows:

30.9 parts of cobaltous sulphate hexahydrate were added to a stirred mixture of 33.9 parts of 1-phenyl-3- methyl-4-(2-hydroxy-5-nitrophenylazo) 5 pyrazolone, 150 parts of water and 200 parts of an aqueous solution of ammonium hydroxide of specific gravity 0.89, and the resulting mixture was stirred at 15 C. for 20 hours. The precipitated 1:1-cobalt complex was then filtered ofii, washed with water and dried.

Example 2 In place of the 21.95 parts of 1-(2'-hydroxy-4-sulpho- 6'-nitronaphth-1-ylazo-2-naphthol used in Example 1 there are used 20.2 parts of 2-amino7-(2-hydroxy-5'- nitrophenylazo)-8-naphthol-6-sulphonic acid whereby a product is obtained which consists essentially of the 1:2- cobalt complex of the formula:

When this complex is reacted with acryloyl chloride in aqueous medium the corresponding N-acryloyl derivative is obtained, which when applied to woollen textile materials from a neutral or slightly acid dyebath yields dark brown shades possessing excellent fastness to wet treatments.

Example 3 A mixture of 21.8 parts of the 1:1-cobalt complex of 1 phenyl 3-methyl-4-(2'-hydroxy-5'-chlorophenylazo)- S-pyrazolone containing coordinated molecules of am monia, 21.15 parts of l (4-a.minophenyl)-3-methyl-4- (2 hydroxy 3 sulpho-S-chlorophenylazo)-5-pyrazolone, 5 parts of active carbon, 500 parts of water and 1000 parts of formarnide is adjusted to a pH of 8.0 by the addition of sodium carbonate, and the mixture is then stirred for 15 minutes at C. The mixture is filtered, and the resulting filtrate poured into a solution of 1000 parts of sodium chloride in 4500 parts of water. The precipitated cobalt complex is then filtered off, washed with an aqueous solution of sodium chloride and dried.

The compound so obtained consists of the 1:2-cobalt complex of the formula:

(m NH:

Lei

When the complex is reacted with acryloyl chloride in aqueous medium the corresponding N-acryloyl derivative is obtained, which, when applied to Woollen textile materials from a neutral or slightly acid dyebath, yields orange shades possessing excellent fastness to light and to wet treatments.

The 1:1-cobalt complex used in the above example was itself obtained by stirring, for 20 hours at 15 C., a mixture of 1 phenyl 3 methyl 4 (2 hydroxy 5'- chlorophenylazo)-5-pyrazolone, cobaltous sulphate, an aqueous solution of ammonium hydroxide and formamide in an inert atmosphere, and filtering off the 1:1-cobalt complex which was precipitated.

Example 4 In place of the 22.35 parts of the 1:1-cobalt complex used in Example 1 there are used 19.25 parts of the 1:1- cobalt complex of 1 (2 hydroxy 5 nitrophenylazo)- Z-naphthol containing coordinated ammonia molecules whereby there is obtained the 1:2-cobalt complex of the formula:

When applied to woolen textile materials from a neutral or slightly acid dyebath the complex yields reddishbrown shades possessing excellent fastness to light and to wet treatments.

The 1:1-cobalt complex used in this example was obtained by the method given in Example 1 for the preparation of the lzl-cobalt complex except that the 33,9 parts of 1 phenyl 3 methyl 4 (2' hydroxy 5- nitrophenylazo)-5-pyrazolone were replaced by an equivtable, are reacted with the metallisable a'zo compounds listed in the fourth column of the table by methods similar to those described in the previous examples.

The fifth column of the table indicates the shades ob- Ex. 1:1-Cobalt complex of- Amine Metallisable Azo Compound Shade 5 1-(m-aminophenyl)-3-carboxy-4-(2-hydroxy-5-sul- Ammonia 2-amino6-(2-hydroxy-3-sulpho-5-nitrophenylazo)- Reddishphophenylazo)-5-pyrazolone. 5-naphthol-1z7-disulphonic acid. brown. 6 .do .do 2-ammo7-(2-hydroxy-3-sulpho-5-nitrophenylazo)- Do.

S-naphthol-G-sulphonic acid. 7 1-(m-aminophenyl)-3-Inethy1-4-(2-hydroxy-5-suldo .do Brown,

phophenylazo)-5-pyrazolone. 8 do .do 1-81111110-7-(2'-hydr0xy-5' nitrophenylazo)-8-naph- Greyishthol-3z6-disulphonic acid. green, 9 1-(p-sulphophenyl)-3-methyl-4-(2-hydroxy-5-sul- ...do l-aminO-7-(2'-hydroxy-3-sulpho-5-nitrophenylazo).

phophenylazo)-5-pyrazolone. 8-naphtho1-3: 6-disulphoni0 acid. 10 do .do 2-amino-6-(o-carboxyphenylazo)-5-naphthol-7-sul- Brown.

phonic acid. 11..-. ..-do .do 1-(Q-Su1pl10ph9ny1)'3-methyl-4-(2-hydroxy-3:5- Orange.

dlsulphophenylazo)-5-pyrazolone. 12 l-arm'nofl-(2-hydroxy-5-nitrophenylazo)-8 naph- .do l-amino-7-(o-carboxyphenylazo)-8-naphthol-3z6- Blue.

thol-3:6-disulphonic acid. disulphonic acid. 13 d D0. 14 2-arn1no-7-(2-hydroxy-3-c ulphophenylazo)- Violet.

8-naphthol-6-sulphonic acid. 2-amin0-6-(2-carboxyphenylazo)-naphth0l-7- Grey.

snlphonic acid. 16 1-(p-sulphopheny1)-3-methyl-4-(2'-hydroxy-3:5- .do l-(p-sulphopheny )-3-methyl-4-(o-carboxyphenyl- Brown.

disulphophenylazo)-5-pyrazolone. azo)-5-pyrazolone. 17 1-amino-7-(o-carboxyphenylazo)-8-naphthol-3: 6- do .do Grey.

disnlphonic acid. 1s a-(2'-hydroxy-3:5-disulphophenyl-az0)-B-ket0-N- do 2-am1no-6-(o-carboxyphenylazo)-5-naphthol-7- Brown.

phenyl-n-butyramide. sulphonic acid. 19 do -do 1-am1n0-7-(2-hydroxy-3-sulphd5-nitrophenylazo)- Green.

8-naphthol-3: fi-disulphonic acid. 20 do d0 1-(p-sulphophenyl)-3-methyl-4-(2-hydroxy-5- Reddishsulphophenylazo)-5-pyrazolone. yellow. 21 a-(2-hydroxyphenylazo)-fi-keto-N-phenyl-n- Pyridine 1-(p-ammo henyD-3-methyl-4-(2-hydroxy-3'- Do.

butyramide. sulpho-5 -ch1orophenylazo)-5-pyrazolone. 22 1-phenyl-3-methyl4-(2-hydroxy-5-nitr0phenylazo)- Methylamine. 1-(2-hydr0xy4-sulpho-6-nitronaphth-1-ylazo)-2- Reddish- 5- yrazolone. pht lbrown. 23 lX-(2 -hydroxy-5-chlorophenylazo)-B-keto-N-phenyl- Ammonia a-(2-hydroxy-5-snlphophcnylazo)-;i-keto-N-phenyl- Yellow.

n-butyramide. n-butyramide. 24 do .do a(2-hyd1'0Xy-3-chl0r0-5-5ulph0phenylazo) 3-keto- D0.

N-phenyl-n-butyramide. 25 -.do 1-phenyl-3-methyl4-(2-hydroxy 5'-sulphophenyl- Brownishazo)-5-pyrazolone. y ll 26 1-(2-hydroxy-4nitrophenylazo)-2-naphthol 2-acetylamino-6-(2-hydroxy-4-nitrophenylazo)-5- Navy-Blue.

naphthol-7-sulphonic acid. 7- -30815ylamln07-(2-hydroxy-4-nitrophenylazo)-8- D naphthol-fi-sulphonic acid. 28"" 1-phenyl-3-methyl-4-(2-hydroxyi-nitrophenylazo)- 2-acetylamino-6-(o-carboxyplicnylazo)-5-naphtl1ol-7- Orange.

5-pyrazolone. sulphonic acid. 2 '-hydIOXy-3-SlllphO-5-chl0rophenylazo)-fl-keto N-phenyl-n-butyramide. 30 1-[2'-hydroxy-3-(3-sulphamylphenylazo)-5- l-acetylamino-8-(2-hydroxy4-nitrophenylazo)-7- Blue.

methylphenylazo]-2-naphthol. naphthol. 31 .do 1-[2-hydr0xy-5-(3 -sulphamylphenylazo)-phenyl- Bro n.

az01-2-naphthol. 32 1-[ZJiydrOXgg-g3"-sulphamylphenylazo)phenyl- 1-[t2l;-liydroxy-4-nitro-5-chlorophenylazo)-2-naph- Blue.

azo -2-nap o 0 33 a-(2-hydroxy-5-su lphophenylazo)-fi-keto-N-phenyl- 1-[2-hydr oxy-3-( sulpharnylphenylazo)-5-methyl- Yellowishn-butyramide. phenyl-azol-Z-naphthol. brow 34 l-phenyl-3-methyl-4-(2'-hydroxy-5-mtrophenyl- 2:2-dihydroxy-5-methylazobenzene-5-sulphonic Do.

az0)-5-pyrazolone. acid. 35 l-phenyl-3-n1ethyl-4-(2-hydroxy-5-chlorophenyl- 2:2-dlhydroxy-5-methyl-5-chlor0azobenzene-5- Brown.

azo-5-pyrazolone. sulphonic acid. 36 a-(2-hydroxyphenylazo)*fl-keto-N-phenyLn-butyr- Methylamine l-(4-a1ninophenyl)-3-methyl-4-(2-hydroxy-5'- Reddish. a ide, chloro-3-sulphophenylazo)-5-pyrazolone. yellow. 37 d do 2:2-dhydroxy-5-methylazobenzene-5-snlphonic Yillowishaci rown. 38 l-phenyl-3-methyl-4-(2-hydroxy-5-chlorophenyl- .d0 1-(4-aminophenyl)-3-methyl-4-(2-hydroxy-5- Orange.

azo)-5-pyrazolone. chloro-3-sulphophenylazo)-5-pyrazolone. 39 1-phenyl-3-methyl-4-(2-hydroxy-5-mtrophenylazo)- D1methylamme. 1-(2-hydroxy-6nitro-4-sulphonaphth-1-ylazo)-2- Reddish- 5pylaZ0l0ne. naphthol. brown. 40 do .410 2-acetylamino-7-(2-hydroxy-5-nitrophenylazo)-8- Dark brown.

naphthol-G-sulphonic acid. 41 l-phenyl-3-methyl-4-(2-hydr0xy-5-chlorophenyl- Ethylamme l-(4-a.minophenyl)-3-methyl-4-(2-hydroxy-5- Orange.

azo)-5-pyrazolone.

alent amount of 1 (2' hydroxy 5 nitrophenylazo)- Z-naphthol.

The table above gives further examples which further illustrate the process of the invention for the production of 1:2-c0balt complexes of matallisable azo dyestuifs. In this table the lzl-cobalt complexes of the metallisable azo compounds listed in the second column of the table and containing coordinated molecules of the ond column of the table with cobaltous sulphate in the presence of the amines listed in the third column of the What we claim is:

1. An improved process for the manufacture of the 1:2- balt complexes which, in the form of the free acids, are

represented by the formula:

wherein A and A" each independently represent a radical selected from the group consisting of phenyiene and consisting of ammonia and a monoamine selected from naphthalene; the group consisting of primary and secondary alkyl- Z and Z which are attached to A and A" respectiveamines, primary and secondary arylamines and heteroly in ortho position to the azo group are independcyclic compounds selected from the group consisting of ently selected from the class consisting of -O pyridine, piperidine, isoquinoline, quinoline, p-picoliue,

and COO-; morpholine and 'y-picoline, the coordinate bonds which B and B each independently represent a radical of link the cobalt atom to R R and R being bonded to the a coupling component selected from the group connitrogen atoms present in R R and R sisting of phenol, naphthol, acylacetarylamide and v5- 2. Process as claimed in claim 1 wherein the reaction is pyrazolone, the cobalt atom being attached to B carried out at'a pH between 7.0 and 9.0. and B" through the oxygen atoms which are situated in ortho position to the coupling positions; and is carried out in the presence of active carbon.

provided that at least one of A, Z and B is not 4. Process as claimed in claim 1 wherein one of the identical with A", Z and B respectively; which 1:1-coba1t complex and the metallisable azo compound comprises reacting a 1:1-coba1t complex of the containsasingle sulphonic acid group.

formula:

R1 R2 R3 References Cited gg UNITED STATES PATENTS L IQ 2,871,233 1/1959 Pfitzner et a1 26-145 X with a metallisable azo compound of the formula: FOREIGN PATENTS f 612,466 1/1961 Canada. i1"N=N-B" 830,970 3/ 1960 Great Britain.

wherein A, A, B, B", Z and Z have the meanings stated and R R and R are each selected from the class FLOYD HIGEL Primary Examine"- 3. Process as claimed in claim 1 wherein the reaction 

1. AN IMPROVED PROCESS FOR THE MANUFACTURE OF THE 1:2COBALT COMPLESES WHICH, IN THE FORM OF THE FREE ACIDS, ARE REPRESENTED BY THE FORMULA: 